Electrochemical studies of gold and chloride in ionic liquids

For the first time, the electrochemistry of gold has been studied in detail in a 'second-generation', non-haloaluminate, ionic liquid. In particular, the electrochemical behaviour of Na[AuCl4] has been investigated in 1-butyl-3-methylimidazolium bis{(tifluoromethyl)sulfonyl} imide, [C(4)mim][NTf2], over gold, platinum and glassy carbon working electrodes. The reduction of [AuCl4](-) initially forms [AuCl2](-) before deposition on the electrode as Au(0). To enable stripping of deposited gold or electrodissolution of bulk gold, the presence of chloride, trichloride or chlorine is required. Specifically trichloride and chlorine have been identified as the active species which preferentially form Au(I) and Au(III), respectively.

Effect of activated carbon xerogel pore size on the capacitance performance of ionic liquid electrolytes

The use of ionic liquid (IL) electrolytes promises to improve the energy density of electrochemical capacitors (ECs) by allowing for operation at higher voltages. Several studies have also shown that the pore size distribution of materials used to produce electrodes is an important factor in determining EC performance. In this research the capacitative, energy and power performance of ILs 1-ethyl-3- methylimidazolium tetrafluoroborate (EMImBF4), 1-ethyl-3-methylimidazolium dicyanamide (EMImN(CN)2), 1,2-dimethyl-3-propylimidazolium bis(trifluoromethylsulfonyl)imide (DMPImTFSI), and 1-butyl-3-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate (BMPyT(F5Et)PF3) were studied and compared with the commercially utilised organic electrolyte 1M tetraethylammonium tetrafluoroborate solution in anhydrous propylene carbonate (Et4NBF4–PC 1 M). To assess the effect of pore size on IL performance, controlled porosity carbons were produced from phenolic resins activated in CO2. The carbon samples were characterised by nitrogen adsorption– desorption at 77 K and the relevant electrochemical behaviour was characterised by cyclic voltammetry, galvanostatic charge–discharge and electrochemical impedance spectroscopy. The best capacitance performance was obtained for the activated carbon xerogel with average pore diameter 3.5 nm, whereas the optimum rate performance was obtained for the activated carbon xerogel with average pore diameter 6 nm. When combined in an EC with IL electrolyte EMImBF4 a specific capacitance of 210 F g1 was obtained for activated carbon sample with average pore diameter 3.5 nm at an operating voltage of 3 V. The activated carbon sample with average pore diameter 6 nm allowed for maximum capacitance retention of approximately 70% at 64 mA cm2.

The electrochemical oxidation and reduction of nitrate ions in the room temperature ionic liquid [C(2)mim][NTf2]; the latter behaves as a 'melt' rather than an 'organic solvent'

The electrochemical oxidation of 1-butyl-3-methylimidazolium nitrate [C(4)mim][NO3] was studied by cyclic voltammetry in the room temperature ionic liquid (RTIL) 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide [C(2)mim][NTf2]. A sharp peak was observed on a Pt microelectrode (d = 10 mu m), and a diffusion coefficient at infinite dilution of ca. 2.0 x 10(-11) m(2) s(-1) was obtained. Next, the cyclic voltammetry of sodium nitrate (NaNO3) and potassium nitrate (KNO3) was studied, by dissolving small amounts of solid into the RTIL [ C2mim][ NTf2]. Similar oxidation peaks were observed, revealing diffusion coefficients of ca. 8.8 and 9.0 x 10(-12) m(2) s(-1) and solubilities of 11.9 and 10.8 mM for NaNO3 and KNO3, respectively. The smaller diffusion coefficients for NaNO3 and KNO3 (compared to [C(4)mim][NO3]) may indicate that NO3- is ion-paired with Na+ or K+. This work may have applications in the electroanalytical determination of nitrate in RTIL solutions. Furthermore, a reduction feature was observed for both NaNO3 and KNO3, with additional anodic peaks indicating the formation of oxides, peroxides, superoxides and nitrites. This behaviour is surprisingly similar to that obtained from melts of NaNO3 and KNO3 at high temperatures ( ca. 350 - 500 degrees C), and this observation could significantly simplify experimental conditions required to investigate these compounds. We then used X-ray photoelectron spectroscopy (XPS) to suggest that disodium( I) oxide (Na2O), which has found use as a storage compound for hydrogen, was deposited on a Pt electrode surface following the reduction of NaNO3.

The electrochemical reduction of the purines guanine and adenine at platinum electrodes in several room temperature ionic liquids

The reduction of guanine was studied by microelectrode voltammetry in the room temperature ionic liquids (RTILs) N-hexyltriethylammonium his (trifluoromethanesulfonyl) imide [N-6.2.2.2][N(Tf)(2)], 1-butyl-3-methylimidazolium hexafluorosphosphate [C(4)mim] [PF6], N-butyl-N-methyl-pyrrolidinium bis(trifluoromethanesulfonyl)imide [C(4)mpyrr][N(Tf)(2)], 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide [C-4mim][N(TF)(2)], N-butyl-N-methyl-pyrrolidinium dicyanamide [C(4)mpyrr][N(NC)(2)] and tris(P-hexyl)-tetradecylphosphonium trifluorotris(pentafluoroethyl)phosphate [P-14,P-6,(6,6)][FAP] on a platinum microelectrode. In [N-6,N-2,N-2,N-2][NTf2] and [P-14,P-6,P-6.6][FAP], but not in the other ionic liquids studied, guanine reduction involves a one-electron, diffusion-controlled process at very negative potential to produce an unstable radical anion. which is thought to undergo a dimerization reaction, probably after proton abstraction from the cation of the ionic liquid. The rate of this subsequent reaction depends on the nature of the ionic liquid, and it is faster in the ionic liquid [P-14,P-6,P-6.6[FAP], in which the formation of the resulting dimer can be voltammetrically monitored at less negative potentials than required for the reduction of the parent molecule. Adenine showed similar behaviour to guanine but the pyrimidines thymine and cytosine did not; thymine was not reduced at potentials less negative than required for solvent (RTIL) decomposition while only a poorly defined wave was seen for cytosine. The possibility for proton abstraction from the cation in [N-6,N-2,N-2,N-2],[NTF2] and [P-14,P-6,P-6.6][FAP] is noted and this is thought to aid the electrochemical dimerization process. The resulting rapid reaction is thought to shift the reduction potentials for guanine and adenine to lower values than observed in RTILs where the scope for proton abstraction is not present. Such shifts are characteristic of so-called EC processes where reversible electron transfer is followed by a chemical reaction. (C) 2009 Elsevier B.V. All rights reserved.

The effects of temperature on the performance of electrochemical double layer capacitors

An electrochemical double layer capacitor test cell containing activated carbon xerogel electrodes and ionic liquid electrolyte was tested at 15, 25 and 40 OC to examine the effect of temperature on electrolyte resistance (RS) and equivalent series resistance (ESR) measured using impedance spectroscopy and capacitance using charge/discharge cycling. A commercial 10F capacitor was used as a comparison. Viscosity, ionic self-diffusion coefficients and differential scanning calorimetry measurements were used to provide an insight into the behaviour of the 1,2-dimethyl-3-propylimdazolium electrolyte. Both RS and ESR decreased with increasing temperature for both capacitors. Increasing the temperature also increased the capacitance for both the test cell and the commercial capacitor but proportionally more for the test cell. An increase in temperature decreased the ionic liquid electrolyte viscosity and increased the self diffusion coefficients of both the anion and the cation indicating an increase in dissociation and increase in ionic mobility.

Evaluation of Corrosion Fatigue Behaviour of Laser-welded NiTi Alloys using Bending Rotation Fatigue Test in Simulated Body Fluid

Shape memory NiTi alloys have been used extensively for medical device applications such as orthopedic, dental, vascular and cardiovascular devices on account of their unique shape memory effect (SME) and super-elasticity (SE). Laser welding is found to be the most suitable method used to fabricate NiTi-based medical components. However, the performance of laser-welded NiTi alloys under corrosive environments is not fully understood and a specific focus on understanding the corrosion fatigue behaviour is not evident in the literature. This study reveals a comparison of corrosion fatigue behaviour of laser-welded and bare NiTi alloys using bending rotation fatigue (BRF) test which was integrated with a specifically designed corrosion cell. The testing environment was Hanks’ solution (simulated body fluid) at 37.5oC. Electrochemical impedance spectroscopic (EIS) measurement was carried out to monitor the change of corrosion resistance at different periods during the BRF test. Experiments indicate that the laser-welded NiTi alloy would be more susceptible to the corrosion fatigue attack than the bare NiTi alloy. This finding can serve as a benchmark for the product designers and engineers to determine the factor of safety of NiTi medical devices fabricated using laser welding.

Comparative studies between classic and wireless electrochemical promotion of a Pt catalyst for ethylene oxidation

A comparative study between a classic and a wireless electrochemical promotion experiment was undertaken as a tool towards the better understanding of both systems. The catalytic modification of a platinum catalyst for ethylene oxidation was studied. The catalyst was supported on yttria-stabilised-zirconia (YSZ), a known pure oxide ion conductor, for the classic experiment and La _0.6Sr_0.4Co_0.2Fe_0.8O _3-δ-a mixed oxide ion electronic conductor-was used for the wireless experiment. The two systems showed certain similarities in terms of the reaction classification (in both cases electrophobic behaviour was observed) and the promotion mechanism. Significant difference was observed in the time scales and the reversibility of the induced rate modification. © 2008 Springer Science+Business Media B.V.

Electrochemical promotion of a metal catalyst supported on a mixed-ionic conductor

It has been found that the catalytic activity and selectivity of a metal film deposited on a solid electrolyte could be enhanced dramatically and in a reversible way by applying an electrical current or potential between the metal catalyst and the counter electrode (also deposited on the electrolyte). This phenomenon is know as NEMCA [S. Bebelis, C.G. Vayenas, Journal of Catalysis, 118 (1989) 125-146.] or electrochemical promotion (EP) [J. Prichard, Nature, 343 (1990) 592.] of catalysis. Yttria-doped barium zirconate, BaZr_0.9Y_0.1O_{3 - α} (BZY), a known proton conductor, has been used in this study. It has been reported that proton conducting perovskites can, under the appropriate conditions, act also as oxide ion conductors. In mixed conducting systems the mechanism of conduction depends upon the gas atmosphere that to which the material is exposed. Therefore, the use of a mixed ionic (oxide ion and proton) conducting membrane as a support for a platinum catalyst may facilitate the tuning of the promotional behaviour of the catalyst by allowing the control of the conduction mechanism of the electrolyte. The conductivity of BZY under different atmospheres was measured and the presence of oxide ion conduction under the appropriate conditions was confirmed. Moreover, kinetic experiments on ethylene oxidation corroborated the findings from the conductivity measurements showing that the use of a mixed ionic conductor allows for the tuning of the reaction rate. © 2006 Elsevier B.V. All rights reserved.

Corrosion Fatigue Behaviour of Laser-welded Shape Memory NiTi Wires in a Simulated Body Fluid

Corrosion fatigue is a fracture process as a consequence of synergistic interactions between the material structure, corrosive environment and cyclic loads/strains. It is difficult to be detected and can cause unexpected failure of engineering components in use. This study reveals a comparison of corrosion fatigue behaviour of laser-welded and bare NiTi wires using bending rotation fatigue (BRF) test coupled with a specifically-designed corrosion cell. The testing medium was Hanks’ solution (simulated body fluid) at 37.5 oC. Electrochemical impedance spectroscopic (EIS) measurement was carried out to monitor the change of corrosion resistance of sample during the BRF test at different periods of time. Experiments indicate that the laser-welded NiTi wire would be more susceptible to the corrosion fatigue attack than the bare NiTi wire. This study can serve as a benchmark for the product designers and engineers to understand the corrosion fatigue behaviour of the NiTi laser weld joint and determine the fatigue life safety factor for NiTi medical devices/implants involving laser welding in the fabrication process.